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Mineral induced formation of sugar phosphates.

Glycolaldehyde phosphate, sorbed from highly dilute, weakly alkaline solution into the interlayer of common expanding sheet structure metal hydroxide minerals, condenses extensively to racemic aldotetrose-2,4-diphosphates and aldohexose-2,4,6-triphosphates. The reaction proceeds mainly through racemic erythrose-2,4-phosphate, and terminates with a large fraction of racemic altrose-2,4,6-phosphate. In the absence of an inductive mineral phase, no detectable homogeneous reaction takes place in the concentration- and pH range used. The reactant glycolaldehyde phosphate is practically completely sorbed within an hour from solutions with concentrations as low as 50 micrometers; the half-time for conversion to hexose phosphates is of the order of two days at room temperature and pH 9.5. Total production of sugar phosphates in the mineral interlayer is largely independent of the glycolaldehyde phosphate concentration in the external solution, but is determined by the total amount of GAP offered for sorption up to the capacity of the mineral. In the presence of equimolar amounts of rac-glyceraldehyde-2-phosphate, but under otherwise similar conditions, aldopentose-2,4,-diphosphates also form, but only as a small fraction of the hexose-2,4,6-phosphates.

Acetaldehyde↗

The synthesis of glutamic acid in the absence of enzymes: implications for biogenesis.

This paper reports on the non-enzymatic aqueous phase synthesis of amino acids from keto acids, ammonia and reducing agents. The facile synthesis of key metabolic intermediates, particularly in the glycolytic pathway, the citric acid cycle, and the first step of amino acid synthesis, lead to new ways of looking at the problem of biogenesis.

Alanine↗

Enantioselective autocatalysis. II. Racemization studies on a 1,4-benzodiazepinooxazole derivative.

Since the bromofluoro-1,4-benzodiazepinooxazole derivative I may undergo spontaneous resolution on crystallization from methanol solution, it provides an ideal substrate on which to study the phenomenon of enantioselective autocatalysis involving spontaneous resolution under racemizing conditions (SRURC). In order to augment the understanding of factors which might be important in such a process we have now undertaken to study the racemization of I in more detail by observing its rate under a wide variety of experimental conditions.

Acetic Acid↗

Adsorption of monomers on microspherical structures of thermal heterocomplex molecules from amino acids.

The surface of a microspherical structure formed in the aqueous suspension of thermal heterocomplex molecules made by heating aspartic acid and proline can adsorb basic amino acids such as histidine, lysine and arginine. It can also adsorb adenine, cytosine, adenosine and cytidine. Electrostatic interactions acting between those monomers to be adsorbed and the absorbing surface are responsible for the adsorption.

Adenine↗

Preferential uptake of ammonium ions by zinc ferrocyanide.

The concentration of ammonia from dilute aqueous solution could have facilitated many prebiotic reactions. This may be especially true if this concentration involves incorporation into an organized medium. We have shown that (unlike iron(III) ferrocyanide) zinc ferrocyanide,Zn2Fe(CN)6 xH2O, preferentially takes up ammonium ions from 0.01 M NH4Cl to give the known material Zn3(NH4)2[Fe(CN)6]2 xH2O, even in the presence of 0.01 M KCl. KCl alone gave Zn3K2[Fe(CN)6]2 xH2O. Products were characterized by elemental (CHN) analysis and powder X-ray diffraction (XRD). We attribute the remarkable specificity for the ammonium ion to the open framework of the product, which offers enough space for hydrogen-bonded ammonium ions, and infer that other inorganic materials with internal spaces rich in water may show a similar preference.

Ammonia↗

Enantioselective autocatalysis. III. Configurational and conformational studies on a 1,4-benzodiazepinooxazole derivative.

We report here on configurational and conformational studies undertaken on the bromofluoro-1,4-benzodiazepinooxazole derivative I, which has previously been found capable of undergoing total spontaneous resolution under racemizing conditions. Due to its bridgehead N-atom I may exist in any of four diastereomeric forms, CRNR (or CSNS) and CRNS (or CSNR). Molecular mechanics calculations revealed that in their lowest energy conformations the CRNR (or CSNS) diastereomers were favored over the CRNS (or CSNR) diastereomers by some 3.42 kcal/mol, while semi-empirical quantum mechanical calculations indicated heats of formation also favoring the CRNR (or CSNS) diastereomers by 3.83 kcal/mol. The 1H NMR spectra of the three crystalline modifications (alpha, beta and gamma) of I were examined in acetone, and found to be identical. These data, combined with the results of the above calculations, suggest that I exists in methanol or methanol-acetone solutions as the CRNR (or CSNS) enantiomer prior to its racemization.

Anti-Anxiety Agents↗

Prebiotic peptide-formation in the solid state. I. Reactions of benzoate ion and glycine with adenosine 5'-phosphorimidazolide.

The reactions of benzoate ion and of glycine with adenosine 5-phosphorimidazolide have been investigated. Benzoate reacts first to give the anhydride, benzoyl-adenylate, which, in the presence of excess imidazole, reacts further to give the 2'- and 3'-esters of adenosine 5'-phosphate. Glycine also first attacks the imidazolide to give an anhydride, but this compound may react further either to give 2- and 3'-esters or to form peptides, depending on the reaction conditions.

Adenine Nucleotides↗

Energetics of peptide bond formation at elevated temperatures.

The free energies of formation of the peptide bond between carbobenzoxy-glycine and L-phenylalanine amide in aqueous solution at temperatures up to 60 degree C were calculated from experimentally determined equilibrium constants. The reaction was catalyzed by a thermophylic enzyme. The thermodynamic energy barrier to peptide bond formation was found to decrease with increasing temperature: the standard free energy of peptide bond formation did appear to become negative in the region of 60 degrees C. The possible significance of these results for peptide bond formation under prebiotic conditions is discussed.

Biological Evolution↗

The catalysis of nucleotide polymerization by compounds of divalent lead.

Soluble lead salts and a number of lead-containing minerals catalyze the formation of oligonucleotides from nucleoside 5'-phosphorimidazolides. The effectiveness of lead compounds correlates strongly with their solubility. Under optimal conditions we were able to obtain 18% of pentamer and higher oligomers from ImpA. Reactions involving ImpU gave smaller yields.

Biological Evolution↗

Reactions of aminomalononitrile with electrophiles.

Aminomalononitrile (HCN trimer) reacts with electrophiles such as aldehydes and acrylonitrile under very mild conditions of temperature and pH to produce intermediates which, after acid hydrolysis, yield amino acids. The following amino acids have been identified and quantitated: glycine, D, L-erythro- and D, L-threo-beta - hydroxyaspartic acids, D, L glutamic acid, and D, L-threonine and allo-threonine. The mechanism of their formation and the possible significance of these reactions in prebiotic syntheses are discussed.

Amines↗

Prebiotic peptide-formation in the solid state. III. Condensation reactions of glycine in solid state mixtures containing inorganic polyphosphates.

The reactions of glycine with inorganic polyphosphates in the solid state have been studied. The formation of peptides up to the decamer occurs at moderate temperatures(r.t.-100 degrees C) in the presence of imidazole and magnesium chloride. If adenosine 5' -monophosphate is added to the reaction mixture, 2'(3') -o-glycyl adenosine 5'-monophosphate is also obtained. These reactions could have occurred on the primitive earth.

Adenine Nucleotides↗

The prebiotic synthesis of deoxthymidine oligonucleotides. II. Comparison of condensing agents.

A reaction which oligomerizes nucleotides under possible prebiotic conditions has been characterized. Nucleoside monophosphate in the presence of cyanamide at acid pH condenses to form dithymideine pyrophosphate and phosphodiester bonded compounds. Imidazole compounds and activated precursors such as nucleoside triphosphate are not necessary for this ologomerization reaction which produces primarily cyclic ologonucleotides.

Alkaline Phosphatase↗

Cyanamide mediated synthesis under plausible primitive earth conditions. VI. The synthesis of glycerol and glycerophosphates.

The formation of glycerol occurs when a solution of DL-glyceraldehyde is heated in the presence of hydrogen sulfide at room temperature. DL-glyceraldehyde and dihydroxyacetone treated with hydrazine, as well as DL-glyceraldehyde incubated with formaldehyde are also partially converted to glycerol. The yields of the above reactions are from approximately 1% to about 3%. The formation of glycerophosphates occurs when glycerol is heated with ammonium dihydrogen phosphate and either urea or cyanamide. The yield of glycerophosphates is about 30%, most of which is sn-glycero-1 (3)-phosphate. These findings indicate that glycerol and sn-glycero-3-phosphate, which are moieties of glycerolipids, could have been formed under conditions which may have prevailed on the primitive Earth.

Biological Evolution↗